The differential swelling and bending of multilayer polymeric films due to the dissimilar uptake of volatile organic compounds (VOCs; n-hexane, limonene) in the different layers was studied. Motions of thin polyethylene films triggered by the penetrant were investigated to learn more about how their deformation is related to VOC absorption. Single layers of metallocene or low-density polyethylene, and multilayers (2-288-layers) of these in alternating positions were considered. Single-, 24-, and 288 layer films displayed no motion when uniformly subjected to VOCs, but they could display simple curving modes when only one side of the film was wetted with a liquid VOC. Two-layer films displayed simple bending when uniformly subjected to VOCs due to the different swelling in the two layers, but when the VOC was applied to only one side of the film, more complex modes of motion as well as dynamic oscillations were observed (e.g., constant amplitude wagging at 2 Hz for ca. 50 s until all the VOC had evaporated). Diffusion modeling was used to study the transport behavior of VOCs inside the films and the different bending modes. Finally a prototype VOC sensor was developed, where the reproducible curving of the two-layer film was calibrated with n-hexane. The sensor is simple, cost-efficient, and nondestructive and requires no electricity.

A template transfer method (TTM) and a fiber fixation technique were established for fiber handling and micro tensile stage mounting of aligned and non-aligned electrospun fiber mats. The custom-made template had been precut to be mounted on a variety of collectors, including a rapidly rotating collector used to align the fibers. The method eliminated need for direct physical interaction with the fiber mats before or during the tensile testing since the fiber mats were never directly clamped or removed from the original substrate. By using the TTM it was possible to measure the tensile properties of aligned poly(methyl methacrylate) (PMMA) fiber mats, which showed a 250 % increase in strength and 450 % increase in modulus as compared to a non-aligned system. The method was further evaluated for aligned PMMA fibers reinforced with cellulose (4 wt%) prepared as enzymatically derived nanofibrillated cellulose (NFC). These fibers showed an additional increase of 30 % in both tensile strength and modulus, resulting in a toughness increase of 25 %. The fracture interfaces of the PMMA-NFC fibers showed a low amount of NFC pull-outs, indicating favorable phase compatibility. The presented fiber handling technique is universal and may be applied where conservative estimates of mechanical properties need to be assessed for very thin fibers.

The preparation of superparamagnetic thin fibers by electrospinning dispersions of nanosized magnetite (Fe3O4, SPIO/USPIO) in a PMMA/PEO polymer solution is reported. The saturation magnetization and coercivity were not affected by the concentration (0, 1, 10, 20 wt%) or fiber orientation, showing hysteresis loops with high magnetization (64 A m(2) kg(-1) @ 500 kA m(-1)) and record low coercivity (20 A m(-1)). AC susceptibility measurements vs. temperature at frequencies from 60 to 2 kHz confirmed superparamagnetism. The mechanical properties were only slightly dependent on the particle concentration because the nanoparticles were separately encapsulated by the polymer. A uniform fibre fracture cross section was found at all the investigated particle contents, which suggests a strong interaction at the polymer/particle interface. A theoretical value of the magnetic low field susceptibility was calculated from the Langevin function and compared with measured values. The results show a distinct but concentration-independent anisotropy, favoring magnetization along the fiber orientation with no sign of exchange interaction, explained by complete nanoparticle separation. Superparamagnetism cannot be inferred from particle size alone, so a relevant interpretation and criterion for superparamagnetism is presented, in accordance with Neel's original definition. From the measurements, it can be concluded that magnetic characterization can be used to elucidate the material morphology beyond the resolution of available microscopy techniques (TEM and SEM).

A new type of antimicrobial, biocompatible and toughness enhanced ultra-thin fiber mats for biomedical applications is presented. The tough and porous fiber mats were obtained by electrospinning solution-blended poly (methyl methacrylate) (PMMA) and polyethylene oxide (PEO), filled with up to 25 wt % of Lanasol-a naturally occurring brominated cyclic compound that can be extracted from red sea algae. Antibacterial effectiveness was tested following the industrial Standard JIS L 1902 and under agitated medium (ASTM E2149). Even at the lowest concentrations of Lanasol, 4 wt %, a significant bactericidal effect was seen with a 4-log (99.99%) reduction in bacterial viability against S. aureus, which is one of the leading causes of hospital-acquired (nosocomial) infections in the world. The mechanical fiber toughness was insignificantly altered up to the maximum Lanasol concentration tested, and was for all fiber mats orders of magnitudes higher than electrospun fibers based on solely PMMA. This antimicrobial fiber system, relying on a dissolved antimicrobial agent (demonstrated by X-ray diffraction and Infrared (IR)-spectroscopy) rather than a dispersed and "mixed-in" solid antibacterial particle phase, presents a new concept which opens the door to tougher, stronger and more ductile antimicrobial fibers.

A missing cornerstone in the development of tough micro/nano fibre systems is an understanding of the fibre failure mechanisms, which stems from the limitation in observing the fracture of objects with dimensions one hundredth of the width of a hair strand. Tensile testing in the electron microscope is herein adopted to reveal the fracture behaviour of a novel type of toughened electrospun poly(methyl methacrylate)/poly(ethylene oxide) fibre mats for biomedical applications. These fibres showed a toughness more than two orders of magnitude greater than that of pristine PMMA fibres. The in-situ microscopy revealed that the toughness were not only dependent on the initial molecular alignment after spinning, but also on the polymer formulation that could promote further molecular orientation during the formation of micro/nano-necking. The true fibre strength was greater than 150 MPa, which was considerably higher than that of the unmodified PMMA (17 MPa). This necking phenomenon was prohibited by high aspect ratio cellulose nanocrystal fillers in the ultra-tough fibres, leading to a decrease in toughness by more than one order of magnitude. The reported necking mechanism may have broad implications also within more traditional melt-spinning research.

Conductive natural rubber (NR) nanocomposites were prepared by solvent-casting suspensions of reduced graphene oxide(rGO) or carbon nanotubes (CNTs), followed by vulcanization of the rubber composites. Both rGO and CNT were compatible as fillers in the NR as well as having sufficient intrinsic electrical conductivity for functional applications. Physical (thermal) and chemical reduction of GO were investigated, and the results of the reductions were monitored by X-ray photoelectron spectroscopy for establishing a reduction protocol that was useful for the rGO nanocomposite preparation. Field-emission scanning electron microscopy showed that both nanofillers were adequately dispersed in the main NR phase. The CNT composite displays a marked mechanical hysteresis and higher elongation at break, in comparison to the rGO composites for an equal fraction of the carbon phase. Moreover, the composite conductivity was always ca. 3-4 orders of magnitude higher for the CNT composite than for the rGO composites, the former reaching a maximum conductivity of ca. 10.5 S/m, which was explained by the more favorable geometry of the CNT versus the rGO sheets. For low current density applications though, both composites achieved the necessary percolation and showed the electrical conductivity needed for being applied as flexible conductors for a light-emitting diode.

A major limitation in the development of highly functional hybrid nanocomposites is brittleness and low tensile strength at high inorganic nanoparticle content. Herein, cellulose nanofibers were extracted from wood and individually decorated with cobalt-ferrite nanoparticles and then for the first time molded at low temperature (<120 degrees C) into magnetic nanocomposites with up to 93 wt % inorganic content. The material structure was characterized by TEM and FE-SEM and mechanically tested as compression molded samples. The obtained porous magnetic sheets were further impregnated with a thermosetting epoxy resin, which improved the load-bearing functions of ferrite and cellulose material. A nanocomposite with 70 wt % ferrite, 20 wt % cellulose nanofibers, and 10 wt % epoxy showed a modulus of 12.6 GPa, a tensile strength of 97 MPa, and a strain at failure of ca. 4%. Magnetic characterization was performed in a vibrating sample magnetometer, which showed that the coercivity was unaffected and that the saturation magnetization was in proportion with the ferrite content. The used ferrite, CoFe2O4 is a magnetically hard material, demonstrated by that the composite material behaved as a traditional permanent magnet. The presented processing route is easily adaptable to prepare millimeter-thick and moldable magnetic objects. This suggests that the processing method has the potential to be scaled-up for industrial use for the preparation of a new subcategory of magnetic, low-cost, and moldable objects based on cellulose nanofibers.

Magnetic nanoparticles are the functional component for magnetic membranes, but they are difficult to disperse and process into tough membranes. Here, cellulose nanofibers are decorated with magnetic ferrite nanoparticles formed in situ which ensures a uniform particle distribution, thereby avoiding the traditional mixing stage with the potential risk of particle agglomeration. The attachment of the particles to the nanofibrils is achieved via aqueous in situ hydrolysis of metal precursors onto the fibrils at temperatures below 100 °C. Metal adsorption and precursor quantification were carried out using Induction Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). FE-SEM was used for high resolution characterization of the decorated nanofibers and hybrid membranes, and TEM was used for nanoparticle size distribution studies. The decorated nanofibers form a hydrocolloid. Large (200 mm diameter) hybrid cellulose/ferrite membranes were prepared by simple filtration and drying of the colloidal suspension. The low-density, flexible and permanently magnetized membranes contain as much as 60 wt% uniformly dispersed nanoparticles (thermogravimetric analysis data). Hysteresis magnetization was measured by a Vibrating Sample Magnetometer; the inorganic phase was characterized by XRD. Membrane mechanical properties were measured in uniaxial tension. An ultrathin prototype loudspeaker was made and its acoustic performance in terms of output sound pressure was characterized. A full spectrum of audible frequencies was resolved.

A facile single-step method for obtaining 2–3 nm thick silsesquioxane coatings on metal oxide nanoparticles using different carbon-functional silane precursors is presented. Iron oxide nanoparticles 8.5 nm in diameter were used as a model to evaluate the possibilities of forming different uniform carbon-functional coatings, ranging from hydrophobic to hydrophilic in character. Electron microscopy showed that all the coated nanoparticles could be described as core-shell nanoparticles with single Fe3O4 cores and carbon-functional silsesquioxane shells, without any core-free silicone oxide phase. Steric factors strongly influenced the deposited silicon oxide precursors with octyl-, methyl- or aminopropyl functionalities, resulting in coating densities ranging from 260 to 560 kg/m3. The methyl-functional coatings required several layers of silsesquioxane, 3–4, to build up the 2 nm structures, whereas only 1-2 layers were required for silsesquioxane with octyl groups. Pure silica coatings from tetraethoxysilanes were however considerably thicker due to the absence of steric hindrance during deposition, allowing the formation of 5–7 nm coatings of ca. 10 layers. The coating method developed for the iron oxide nanoparticles was generic and successfully transferred and up–scaled 30 and 325 times (by volume) to be applicable to 25 nm ZnO and 45 nm Al2O3 nanoparticles.

A facile water-based one-pot reaction protocol for obtaining 20 nm thick uniform silica coatings on cellulose nanofibrils (CNFs) is herein presented for the first time. The fully covering silica shells result in the thermal stability of the CNFs improved by ca. 70 degrees C and 50 degrees C under nitrogen and oxygen atmospheres, respectively. Heating of the core-shell hybrid fibres to 400 degrees C results in complete degradation/removal of the CNF cores, and demonstrates an inexpensive route to large-scale preparation of silica nanotubes with the CNFs used as templates. The key to a uniform condensation of silica (from tetraethyl orthosilicate) to cellulose is a reaction medium that permits in situ nucleation and growth of the silica phase on the fibrils, while simultaneously matching the quantity of the condensed silica with the specific surface area of the CNFs. Most coatings were applied to bundles of 2-3 associated CNFs, which could be discerned from their negative imprint that remained inside the silica nanotubes. Finally, it is demonstrated that the coated nanofibrils can be freeze-dried into highly porous silica/cellulose aerogels with a density of 0.005 g cm(-3) and how these hybrid aerogels preserve their shape when extensively exposed to 400 degrees C in air (>6 h). The resulting material is the first reported silica nanotube aerogel obtained by using cellulose nanofibrils as templates.

Green, all-polysaccharide based microcapsules with mechanically robust capsule walls and fast, stimuli-triggered, and switchable permeability behavior show great promise in applications based on selective and timed permeability. Taking a cue from nature, the build-up and composition of plant primary cell walls inspired the capsule wall assembly, because the primary cell walls in plants exhibit high mechanical properties despite being in a highly hydrated state, primarily owing to cellulose microfibrils. The micro capsules (16 +/- 4 mu m in diameter) were fabricated using the layer-by-layer technique on sacrificial CaCO3 templates, using plant polysaccharides (pectin, cellulose nanofibers, and xyloglucan) only. In water, the capsule wall was permeable to labeled dextrans with a hydrodynamic diameter of similar to 6.6 nm. Upon exposure to NaC1, the porosity of the capsule wall quickly changed allowing larger molecules (similar to 12 nm) to permeate. However, the porosity could be restored to its original state by removal of NaCl, by which permeants became trapped inside the capsule's core. The high integrity of cell wall was due to the CNF and the ON/OFF alteration of the permeability properties, and subsequent loading/unloading of molecules, could be repeated several times with the same capsule demonstrating a robust microcontainer with controllable permeability properties.

A controlled aqueous growth of 1 µm flower-shaped ZnO particles with a hierarchical subset of exposed nano-sheets represented by {21̅0} crystal faces, followed by annealing at temperatures up to 1000 °C, is presented. The flower-shaped particles showed superior photocatalytic performance compared to the crystal faces of 20 nm ZnO nanoparticles. The photocatalytic reaction rate of the flower-shaped particles before annealing was 2.4 times higher per m2 compared with that of the nanoparticles with double specific surface area. Crystal surface defects and nano-sized pores within the flower-shaped particles were revealed by porosity measurement and electron microscopy. A heat treatment at 400 °C was found to be optimal for removal of nanoporosity/surface defects and impurities while retaining the hierarchical superstructure. The heat treatment resulted in a photo-degradation efficiency that increased by an additional 43 %, although the specific surface area decreased from 16.7 to 13.0 m2g-1. The enhanced photocatalytic effect remained intact under both acidic and alkaline environments owing to the {21̅0} crystal surfaces, which were less prone to dissolution than the nanoparticles. The photocatalytic performance relied on primarily three factors: the removal of surface impurities, the oxygen termination of the {21̅0} crystal faces, and the promotion of charge carrier lifetime by removal of lattice defects acting as recombination centres. The synthesis presented is an entirely hydrocarbon- and surfactant free ('green') preparation scheme, and the formation of the flower-shaped particles was favored solely by optimization of the reaction temperature after the correct nitrate salts precursor concentrations had been established.

A low temperature (60 degrees C) aqueous synthesis method of high purity ZnO nanoparticles intended as fillers for ultra-low electrical conductivity insulations is described. Particles were prepared under identical conditions from different zinc salts based on nitrate, chloride, sulphate or acetate to compare their abilities to form high yields of sub-50 nm particles with narrow size distribution. The acetate salt gave uniform 25 nm ZnO particles with a conical prism shape. The chloride and sulphate derived particles showed mixed morphologies of nanoprisms and submicron petals, whereas the nitrate salt yielded prisms assembled into well-defined flower shapes with spiky edges. The micron-sized flower shapes were confirmed by Xray diffraction to consist of the smaller prism units. Photoluminescence spectroscopy showed emission in the blue-violet region with little variation depending on precursor salt, suggesting that the spectra were dependent on the primary nanoprism formation and rather independent of the final particle morphology. Microscopy revealed that the salt residuals after the reaction showed different affinity to the particle surfaces depending on the type of salt used, with the acetate creating ca. 20 nm thick hydrated shells; and in falling order of affinity: chloride, sulphate and nitrate. An acetate ion shielding effect during the synthesis was therefore assumed, preventing nanoparticle fusion during growth. Varying the concentrations of the counter-ions confirmed the shielding and only the acetate anions showed an ability to stabilize solitary nanoprisms formation in reaction yields from 2 to 10 g L-1. Ultrasonic particle surface cleaning was significantly more efficient than water replacement, resulting in a stable aqueous dispersion with a high zeta potential of 38.9 mV at pH 8.

KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology. Department of Chemistry and Chemical Engineering, Chalmers University of Technology, Göteborg, 41296, Sweden.

Andersson, Richard L.

KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology.

Tjus, Kåre

Ström, Valter

KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering.

Björk, A.

Olsson, Richard T.

KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology.

Electrocatalysis of wastewater containing ammonia is a promising alternative to chemical and biological water purification for several reasons, one being that energy-rich hydrogen gas is generated as a by-product while the reaction can be strictly controlled to meet demands. An objective has been to reduce the loading of expensive platinum (Pt) in the catalyst electrodes, and to reduce the poisoning of the metal surface during the electrolysis. Herein, the co-deposition of a copper-platinum (Cu-Pt) bimetallic alloy onto carbon filaments, stripped from their polymeric coating, is shown to give an electrocatalytic performance superior to that of pure Pt at a content of less than 3 wt% Pt. The key to the enhanced performance was to take advantage of micrometer-sized carbon filaments to distribute a very large bimetallic alloy surface uniformly over the filaments. The Cu-Pt-alloy-coated filaments also suffer less electrode poisoning than pure Pt, and are bonded more strongly to the carbon fibre due to better mechanical interlocking between the bimetallic alloy and the carbon filaments. High-resolution electron microscopy studies combined with a tuned electro-deposition process made it possible to tailor the catalyst micro/nano morphology to reach a uniform coverage, surrounding the entire carbon filaments. The results are promising steps towards large-scale wastewater treatment, combined with clean energy production from regenerated hydrogen.

Tough fibrous membranes for smoke filtration have been developed from recycled polyethylene terephthalate (PET) bottles by solution electrospinning. The fibre thicknesses were controlled from 0.4 to 4.3 mu m by adjustment of the spinning conditions. The highest fibre strength and toughness were obtained for fibres with an average diameter of 1.0 mu m, 62.5 MPa and 65.8 MJ m(-3), respectively. The X-ray diffraction (XRD) patterns of the fibres showed a skewed amorphous halo, whereas the differential scanning calorimetry (DSC) results revealed an apparent crystallinity of 6-8% for the 0.4 and 1 mu m fibres and 0.2% crystallinity for the 4.3 mu m fibres. Heat shrinkage experiments were conducted by exposing the fibres to a temperature above their glass transition temperature (T-g). The test revealed a remarkable capability of the thinnest fibres to shrink by 50%, which was in contrast to the 4.3 mu m fibres, which displayed only 4% shrinkage. These thinner fibres aka showed a significantly higher glass transition temperature (+15 degrees C) than that of the 4.3 mu m fibres. The results suggested an internal morphology with a high degree of molecular orientation in the amorphous segments along the thinner fibres, consistent with a constrained mesomorphic phase formed during their rapid solidification in the electric field. Air filtration was demonstrated with cigarette smoke as a model substance passed through the fibre mats. The 0.4 mu m fibres showed the most effective smoke filtration and a capacity to absorb 43x its own weight in smoke residuals. whereas the 1 mu m fibres showed the best combination of filtration capacity (32x) and mechanical robustness. The use of recycled PET in the form of nanofibres is a novel way of turning waste into higher-value products.

This article presents a novel type of flame-retardant biohybrid foam with good insulation properties based on wheat gluten and silica, the latter polymerized in situ from hydrolysed tetraethyl orthosilicate (TEOS). This led to the formation of intimately mixed wheat gluten and silica phases, where, according to protein solubility measurements and infrared spectroscopy, the presence of silica had prohibited full aggregation of the proteins. The foams with "built-in" flame-retardant properties had thermal insulation properties similar to those of common petroleum- and mineral-based insulation materials. The foams, with a porosity of 87 to 91%, were obtained by freeze-drying the liquid mixture. Their internal structure consisted of mainly open cells between 2 and 144 mu m in diameter depending on the foam formulation, as revealed by mercury intrusion porosimetry and scanning electron microscopy. The foams prepared with >= 30% TEOS showed excellent fire-retardant properties and fulfilled the criteria of the best class according to UL94 fire testing standard. With increasing silica content, the foams became more brittle, which was prevented by cross-linking the materials (using gluteraldehyde) in combination with a vacuum treatment to remove the largest air bubbles. X-ray photoelectron and infrared spectroscopy showed that silicon was present mainly as SiO2 .

Conductive biofoams made from glycerol-plasticized wheat gluten (WGG) are presented as a potential substitute in electrical applications for conductive polymer foams from crude oil. The soft plasticised foams were prepared by conventional freeze-drying of wheat gluten suspensions with carbon nanotubes (CNTs), carbon black (CB) or reduced graphene oxide (rGO) as the conductive filler phase. The change in conductivity upon compression was documented and the results show not only that the CNT-filled foams show a conductivity two orders of magnitude higher than foams filled with the CB particles, but also that there is a significantly lower percolation threshold with percolation occurring already at 0.18 vol%. The rGO-filled foams gave a conductivity inferior to that obtained with the CNTs or CB particles, which is explained as being related to the sheet-like morphology of the rGO flakes. An increasing amount of conductive filler resulted in smaller pore sizes for both CNTs and CB particles due to their interference with the ice crystal formation before the lyophilization process. The conductive WGG foams with CNTs were fully elastic with up to 10% compressive strain, but with increasing compression up to 50% strain the recovery gradually decreased. The data show that the conductivity strongly depends on the type as well as the concentration of the conductive filler, and the conductivity data with different compressions applied to these biofoams are presented for the first time.

Field-grading materials (FGMs) are used to reduce the probability for electrical breakdowns in critical regions of electrical components and are therefore of great importance. Usually, FGMs are heavily filled (40 vol.%) with semi-conducting or conducting particles. Here, polymer-grafted reduced graphene oxide (rGO) is used as a filler to accomplish percolated networks at very low filling ratios (<2 vol.%) in a semi-crystalline polymer matrix: poly(ethylene-co-butyl acrylate) (EBA). Various simulation models are used to predict the percolation threshold and the flake-to-flake distances, to complement the experimental results. A substantial increase in thermal stability of rGO is observed after surface modification, either by silanization or subsequent polymerizations. The non-linear DC resistivity of neat and silanized rGO and its trapping of charge-carriers in semi-crystalline EBA are demonstrated for the first time. It is shown that the polymer-grafted rGO improve the dispersibility in the EBA-matrix and that the graft length controls the inter-flake distances (i.e. charge-carrier hopping distances). By the appropriate selection of graft lengths, both highly resistive materials at 10 kV mm-1 and FGMs with a large and distinct drop in resistivity (six decades) are obtained, followed by saturation. The nonlinear drop in resistivity is attributed to narrow inter-flake distance distributions of grafted rGO.

Polymer grafts were used to tailor the interphases between ZnO nanoparticles (NPs) and silicone matrices. The final electrical properties of the nanocomposites were tuned by the grafted interphases, by controlling the inter-particle distance and the NP-morphology. The nanocomposites can be used in electrical applications where control of the resistivity is desired. Hansen's solubility parameters were used to select a semi-compatible polymer for grafting to obtain anisotropic NP morphologies in silicone, and the grafted NPs self-assembled into various morphologies inside the silicone matrices. The morphologies in the semi-compatible nanocomposites could be tuned by steering the graft length of poly(n-butyl methacrylate) via entropic matrix-graft wetting using surface-initiated atom-transfer radical polymerization. Image analysis models were developed to calculate the radius of primary NPs, the fraction of aggregates, the dispersion, and the face-to-face distance of NPs. The dielectric properties of the nanocomposites were related to the morphology and the face-to-face distance of the NPs. The dielectric losses, above 100 Hz, for nanocomposites with grafted NPs were approximately one decade lower than those of pristine NPs. The isotropic nanocomposites increased the resistivity up to 100 times compared to that of neat silicone rubber, due to the trapping of charge carriers by the interphase of dispersed NPs and nanoclusters. On the other hand, the resistivity of anisotropic nanocomposites decreased 10–100 times when the inter-particle distance in continuous agglomerates was close to the hopping distance of charge carriers. The electrical breakdown strength increased for compatible isotropic nanocomposites, and the temperature dependence of the resistivity and the activation energy were ∼50% lower in the nanocomposites with grafted NPs. These flexible dielectric nanocomposites are promising candidates for low-loss high-voltage transmission cable accessories, mobile electronic devices, wearables and sensors.